Chemical compound and method of making the same



"Patented Dec. 8, 1931 mom 0. SWALLEN AND WILLIAM J. BANNISTEB, F TEE-BEEAUTE, INDIANA, AE-

SIGHORS T0 COOIAL. SOLVENTS GDREOBATION, 0F TERRE HAUTE, INDIANA,

A CORPORATIQH OF MARELAND CHEEHGAL GOWOUND AND METHOD 0H MAKING THE SAMEHo Drawing.

Our invention relates to the production of a new type of complexchemical compounds which may best be described as metal salts of allrylacid esters of polybasic acid esters of polyhydric alcohols andpolybasic acids.

Zinc butyl glyceryl phthalate may be 'cited as I duced are bestillustrated by the following type equations in which 5 OH R 03: and R OEOH Application filed March 18, 1828. Serial 1T0. 262,985.

0E O-GO-A-OOOE II. ZHQO The next step involves the preparation of thehalf ester of the above compounds by reacting them with appropriatequantities of monohydric alcohols. Uusually, this operation is carriedout as a separate step but in some cases it may be desired to combinethe represent polyhydric alcohols, R-OH a two steps into one operation.

O-GO-A-COOE 0-CO-A-COOH III.

monohydric alcohol, A(COOH) a polybasic acid, and MX a metal salt. v

In preparing a compound of the character in which we are interested, apolyhydric al- 0-0 0-A-CO-O R We have found that the most convenientmethod of obtaining the metal salts of the half esters of thetype'illustrated above is to first prepare the sodium salt and thenreact this compound with a salt of the metal which it is desired tosubstitute for the sodium radical. For example,

/OOOA-OOOR' /O-COACOOR axon +NaOH-o -01; +1no oo0Ao0-oH O-GO-A-CO-ONa Ifthe metal, the salt of which is to be formed, is divalent, the compoundformed during the next reaction may be represented as follows:

211 -01: +MXro-oo-a-co-om When a dihydric alcohol is used in place of atrihydric, the final product similarly becomes of the characterindicated by the formula:

We shall now describe the preparation of a number of specific examples.

, EXAMPLEI Sodium butyl glyceryl phthalate v 138 grams of anhydrousglycerol and 444 grams of phthalic anhydride were heated together forabout one hour at approximately 150 C. After cooling somewhat, L00 gramsof butyl alcohol, 15 grams of concentrated sulphuric acid (catalyst) andabout 400 c. c. of benzol were added to the reaction mix ture and theheating continued. The water formed during the reaction was removed by'distillation, as a component of a constant boiling mixture, with thebenzol. Fresh additions of the benzol were made to the reaction mixturefrom time to time so as to maintain the reaction temperature between 90and 100 C. This was continued until 27 c. c. of water had separated(half the amount required for complete esterification). The product thusformed was poured into water, and neutralized with 550 c. c. of 2.75 N NaOI-I, which gave sodium butyl glyceryl phthalate, together with a smallamount of glyceryl butyl phthalate and some unused butyl alcohol. Thebutyl alcohol was removed by distillation in vacuo, the residue dilutedto about six liters and finally extracted two or three times withbenzolto remove the glyceryl butyl phthalate.

EXAMPLE II Zinc butyl glyceryl phthalate The first step involved thepreparation of sodium butyl glyceryl phthalate, which was obtained asdescribed above under Example I.

Upon the addition of a solution, containing an amount of zinc chloridein excess of that theoretically required, say 240 grams, to thesodiumbutyl glyceryl phthalate, a precipitation of the zmc butylglyceryl phthalate immediately took place. After washing the zinc saltwith distilled water, the latter was separated as completely aspossible, and the salt dissolved in butyl alcohol. The solution wasfiltered and the'water and butyl alcohol then removed by distillation invacuo, until the temperature of the liquid rose to 130 C. y

Zinc butyl glycerl phthalate, obtained in this manner, is a liquid ofthe consistency of soft taffy. Its color is light straw to colorless,depending upon the purity. It is soluble in butyl alcohol, butylacetate, dibutyl phthalate, ethyl alcohol and benzol. It is insoluble inwater and V. M. P. naphtha;

EXAMPLE III Oalczum butyl glyceryl phthalate Sodium butyl glycerylphthalate obtained as described under Example I, was treated with asolution, containing an amount of anhydrous calcium chloride in excessof that theoretically required, say 150 grams. The product obtained waswashed with water, dissolved in butyl alcohol, filtered, and the waterand butyl alcohol finally removed by distillation in vacuo, as describedunder Example II.

The calcium butyl glyceryl phthalate obtained by this method closelyresembled the zinc salt described under Example II above, in all theproperties studied.

EXAMPLE IV Goggmwbutyl glyceryl phthalate Sodium butyl glycerylphthalate obtained as described under Example I, was treated with asolution containing an amount of crystalline copper nitrate in excess ofthat theoretically required, say 300 grams. The precipitate formed wastreated as described under previous examples.

Copper butyl glyceryl phthalate is a clear,

dark, green-blue liquid of the consistency of hard taffy. It is soluble.in butyl alcohol, butyl acetate, dibutyl phthalate, ethyl alcohol andbenzol. It is insoluble in water and V. M. P.'naphtha.

EXAMPLE V Zinc isoamyl glyceryl phthalate Sodium isoamyl glycerylphthalate was closely the corresponding butyl compound in appearance,and properties, except for the fact that it is much less viscous than.the

butyl compound.

In the examples described above, We have chosen to use phthalic acid(anhydride) due to its stability, cheapness, and ease of reaction. Wemay, however, employ other polybasic acids such as terephthalic acid,tartaric acid, citric acid or the like.

Of the various polyhydric alcohols, glycerol and ethylene glycol arebest suited for use. Any monohydric alcohol may be used, lfiui. weprefer to employ normal butyl alco- In place of the sulphuric acid usedas a catalyst in the specific examples above disclosed, otheresterification catalysts such as hydrochloric acid or phosphoric acid,inay be used. In place of benzol, other inert liquids formingconstant-boiling mixtures with water, for examplecarbon tetrachloride--may be employed.

Now having described our invention, we claim the following as new andnovel:

1. A compound havin the following structural formula, in which lt is apolyhydric alcohol having one hydroxyl group which is unchanged; R is amonohydric alcohol group; A is a polybasic acid group; and M is a metal:

O-COAOO-O--MOCOA-C0-0 2. Acom ound havingzthe'following structural formua, in which is a polyhydric alcohol having one hydroxyl group which isunchanged; R is a monohydric alcohol group; A is a polybasic acid group;and M is a metal:

0OO-AO0OR' R'OC0A-O0-O RZ-OH 110 1! o-co-A-ooo-Mooo-A-coo 3. A compoundas described in claim 2, in which said polyhydric alcohol is glycerine,and said polybasic acid is hthalic acid, said prolduct having thefollowing structural formu a:

alkyl acid ester of the polybasic acid ester of a polyhydric alcohol anda polybasic acid.

7 As a new compound, a polyvalent metal salt of the alkyl acid ester ofthe polybasic acid ester of a polyhydric alcohol and a polyv valentacid.

8. As a new compound, the zinc salt ofthe alkyl acid ester of thepolybasic acid ester of a polyhydric alcohol and a polyvalent acid.

9. As a new compound, a metal salt of the butyl acid ester of thepolyvalent acid ester of a polyhydric alcohol and a polybasic acid.

10. As a new compound, a polyvalent metal salt of the butyl acid esterof the polyvalent acid ester of a polyhydric alcohol and a polybasicacid.

11. As a new compound, a metal salt of the alkyl acid ester of themonophthalate ester of a polyhydric alcohol.

12'. As a new compound, a polyvalent metal salt of the butyl acid esterof the monophthalate ester of a polyhydric alcohol.

13. As a new com ound, a metal salt of the butyl acid ester 0 themonophthalate ester of glycerol. i

14. As a new compound, a polyvalent metal salt of the butyl acid esterof the monophthalate ester of glycerol.

15. The process of manufacturing the metal salt of an alkyl acid-esterof the polybasic acid ester of a polyhydric alcohol and a polybasic acidwhich comprises reacting a polybasic acid or anhydride with a polyhydricalcohol; adding a monohydric alcohol, a catalyst, and benzol to thereaction mixture; removing water from the reaction mixture as acomponent of a constant-boiling mixture until the reaction has proceededto the desired extent; washing and neutralizing with analkalinehydroxide, the product thus obtained; and finally reactingsaidneutralized product with a metal salt and recovering the material thusformed.

In testimony whereof we aifix our signatures. v

LLOYD C. SWALLEN. WILLIAM J. BANNISTER.

4. A compound as described in claim 2, in which said polyh dric-alcoholis glycerine, said pplybaslc acid is phthalic acid, and said mono ydricgrou is the butyl group.

5. A compoun as described in claim 2, in which said polyhydric alcoholis glycerine said 01 basic acid is phthalic acid, sai mono y ric groupis the butyl group and the metal is zinc.

6. As a new compound, a metal salt of the

